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Advances in Physics Theories and Applications www.iiste.org

ISSN 2224-719X (Paper) ISSN 2225-0638 (Online)

Vol.17, 2013

23

Synthetic, spectroscopic and Antimicrobial activity of mixed ligand of

some complexes of symmetrical Schiff base and Nicotinamide

Taghreed H. Al.Noor , F.H, Ghanim , I.Y.Majeed

Department of Chemistry.Ibn -Al-Haithem College of Education for pure science

Baghdad University -IRAQ

Corresponding author: e-mail- taghreedalnoor@yahoo,com

Abstract

New symmetrical Schiff base ligand (H2L) is prepared via condensation of hydrazine hydrate and

4-hydroxy-3-methoxybenzaldehyde in ethanol solution at room temperature is reported .

Polydentate mixed ligand complexes were obtained from 1:1:1 molar ratio reactions with metal

ions and H2L, NA on reaction with MCl2 .nH2O salt yields complexes corresponding to the

formulas

[M(L)(NA)2] .

All the complexes are air stable and soluble in water and common organic except benzene .All

complexes are soluble in dimethyl formamide (DMF)and dimethyl sulfoxide (DMSO) solvent.

Comparison of the IR spectra of ligands(H2L) and (NA) and there metal complexes confirm that

Schiff base behave as a dibasic tetradentate ligand towards the central metal ion with an ONNO

donor sequence and nicotinamid . behave as unidentate .

The ligands and their metal complexes were screened for their antimicrobial activity against four

bacteria(gram +ve) and (gram -ve).

Keywords: Complexes; Spectral; symmetrical Schiff base Metal complexes ; Antimicrobial

activities.

1. Introduction

Metal ions play a vital role in a vast number of widely different biological processes. The interaction

of these ions with biologically active ligands, for example in drugs, is a subject of considerable

interest. Some of the biologically active compounds act via chelation [1], but for most of them little

is known about how metal binding influences their activity. Therefore we have been interested in

studying the complexing ability of biologically active ligands. The Schiff base compounds

constitute an important class of ligands which have been extensively studied in coordination

chemistry. The nature of the effect of one ligand and its transmission to another ligand through the

central metal ion is very important in coordination chemistry. [2-3], Antipyrine Schiff base

derivatives can serve as antiparasitic agents and their complexes with platinum (II) and cobalt(II)

ions have been shown to act as antitumour substances [4]. Nicotinamide is known as a component of



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the vitamin B complex as well as a component of the coenzyme, nicotinamide adenine dinucleotide

(NAD). These are more important for transfer of hydrogen in the cell breath. The presence of

pyridine ring in numerous naturally abundant compounds,

adducts of nicotinamide are also scientific interest. Therefore, the structure of nicotinamide has been

the subject of many studies [5-8]

In the area of bioinorganic chemistry the interest in the Schiff base complexes lies in that they

provide synthetic models for the metal-containing sites in metalloproteins/enzymes and also

contributed enormously to the development of medicinal chemistry, radio immunotherapy, cancer

diagnosis and

treatment of tumor [9] and [10]. In addition, some of the complexes containing N and O donor

atoms are effective as stereo specific catalysts for oxidation [11] eduction, hydrolysis, biocidal

activity and other transformations of organic and inorganic chemistry. [12]

2.Materials and Methods

a- All the chemicals and solvents were of analytical grade (supplied by either Merck or Fluka)

received. All the metal ions Mn(II), Co(II),Ni(II), Fe(II) and Cd(II) were of (BDH). They were used

in the form of chlorides without further purification.

b- Instruments: FTIR spectra were recorded as KBr discs using Fourier transform Infrared

Spectrophotometer Shimadzu 24 FTI.R 8400s. Electronic spectra of the prepared complexes were

measured in the region (200- 1100) nm for 10-3

M solutions in DMF at 25ºC using shimadzu-U.V-

160.A Ultra Violet Visible- Spectrophotometer with 1.000 ± 0.001 cm matched quartz cell. While

metal contents of the complexes were determined by Atomic Absorption(A.A)Technique using

Japan A.A-67G Shimadzu. Electrical conductivity measurements of the complexes were recorded at

room temperature for 10-3 M solutions of the samples in DMF using pw9527 Digital conductivity

meter (Philips). Melting points were recorded by using Stuart melting point apparatus . The

Chloride contents of complexes were determined by potentiometric titration method using (686-

Titro processor-665. Dosimat Metrohn Swiss). Magnetic susceptibility measurements were

measured using Bruker magnet BM6 instrument at 298°K following the Faraday's method. The

proposed molecular structure of the complexes were determinated by using chem. office program,

3DX (2006).

C- General procedure for the formation of 4,4'-(hydrazine-1,2-diylidenebis(methan-1-yl-1-

ylidene))bis(2-methoxyphenol)

A solution of hydrazine hydrate(0.833gm,0.5mol) in ethanol 10ml was added dropwise to a stirred

solution of 4-hydroxy-3-methoxybenzaldehyde(5gm,1mol) and the mixture was refluxed for 4h

the reaction mixture was distilled under reduced pressure .The solid obtained was recrystallized

from ethanol.

m .p=158 oc , The color of the product is orange. yield 85.10 %. Anal. Calcd for ligand( H2L)

C = 63.99%, H = 5.37%, N = 9.33%. = Found: C = 61.59%, H = 6.2%, N = 9.78%.



Vol.17, 2013

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HO

O

O+NH2NH2.H2O

2

H3CO OH

N N

OCH3HO

Ethanol

Scheme (1) : Schematic representation of synthesis of the ligand(H2L)

Antibacterial Activities: [12]

The antibacterial activity of the ligands and some there complex were tested on Gram positive

bacteria, Staphylococcus , and Gram negative, Bacillus , Pseudomonas, and Bacillus. The solvent

used was di methyl form amid(DMF) and sample from 1 to 200 µg/ml were used. Ant bactericidal

activities of each compound were evaluated by the well-diffusion method. 1 cm3 of a 24 h broth

culture containing 106 CFU/cm3 was placed in sterile Petri-dishes. Molten nutrient agar(15 cm

3)

kept at ca.45oC was then poured in the Petri-dishes and allowed to solidify. Then holes of 6 mm

diameter were punched carefully using a sterile cork borer and these were completely filled with the

test solutions. The plates were incubated for 24 h at 37oC.

3. Results and discussion

3.1. Characterization of ligand(H2L)

New symmetrical Schiff base ligand (H2L) is prepared via condensation of hydrazine hydrate and

4-hydroxy-3-methoxybenzaldehyde.The physical characterization and micro analytical data of

ligand(H2L) ligand Is given in Table(1), The purity of the Schiff base as formulated, was

established by microanalyses.

3.2. Characterization of mixed ligand complexes:

Generally, the complexes were prepared by reacting the respective metal salts with the ligands using

1:1:2 mole ratio, i.e. one mole of metal salt : one mole of (H2L) and two moles of nicotinamide .

The formula weights and melting points , are given in (Table 1 ).Based on the physicochemical

characteristics, it was found that all the complexes were non-hygroscopic, stable at room

temperature. The molar conductance values of the complexes in solvent at 10-3

M concentration The

observed molar conductance (Table-1) values measured in DMF 10-3

M solution lie in the (4.80-

15.92 ) Ω-1

cm2 mol

-1 range, indicating their nonelectrolytic nature[13].The atomic absorption



Vol.17, 2013

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measurements and chloride ion content (Table-1) for all complexes gave approximated values for

theoretical values. Figure. 1

Fourier-transform infrared spectra and mode of coordination :

The most important infrared spectral bands that provide conclusive structural evidence for the

coordination of the ligands to the central metal ions. The important IR peaks of the complexes are

shown in Table 2. IR spectra of the complexes were interpreted by comparing the spectrum with that

of the free ligand as shown in Table 2. The comparison of the IR spectral bands of the free ligand

(H2L) and its metal complexes indicate that the band at 2993 cm−1 due to intramolecular hydrogen

bonded υυυυ (OH) group in the free ligand spectrum disappeared in all complexes and the υυυυ (CO)

(phenolic) band at 1261 cm−1

, [14].shifted to a higher frequency, suggesting the coordination of

ligand through phenolic oxygen via deprotonation. Besides, the bands at 1600 cm−1

(azomethine

C=N) shifted its position on complexation [15]. In addition to the above bands all the complexes

display the new bands in the far-infrared region (518-617) cm−1

and (418-445) cm−1

were assigned

to υυυυ (M–O) and

υυυυ (M–N) vibrations, respectively [16-18].

The UV-Visible Spectroscopy and Magnetic measurements:

The electronic spectra of the ligands and there complexes were recorded in DMF and their

assignments are given in Table (3). The free ligand H2L spectral data display two bands at 342 nm

(29230cm-1) 357 nm (28011 cm-1)) attributed to π → π* and n → π* transitions and the spectrum of

the free ligand (NA), exhibits absorption peak at (271 nm)(36900 cm-1) which assigned to (π→ π*),

[17] .

The electronic spectrum of the Mn(II) complex exhibited three spin allowed bands in the region

14749cm-1

, 27932cm-1

and 29239 cm-1

assigned to the transitions 6A 1g 4T1g (4G)( υυυυ1), 6A1g

4T2g

(4G) (υυυυ2) and LMCT respectively, indicating octahedral geometry [19-20].The observed

magnetic moment of the Mn(II) complex are 5.04l B.M. corresponding to five unpaired electrons

indicates high spin octahedral environment [20].The electronic spectra of the Fe(II) complex

exhibited three bands at 342nm (29239cm-1), 358 nm ( 27932 cm-1) and 672nm(14880cm-1 ) due to

the presence of a charge transfer (LMCT) and 5T2g → 5E2g. The magnetic moment value of this

complex was found 5.05 BM which was very close to the value of octahedral environment.The

electronic spectra of Co(II) complex displayed three bands at 669nm 1 ( 4947 cm-1

) ,357nm ( 28011

cm-1

) and 342 nm (29239 cm-1

) corresponding to the transitions 4T1g →4T2g(F), due to the

presence of a charge transfer (LMCT)respectively[21]. These transitions as well as the measured

value of magnetic moment 4.12 BM suggested the octahedral geometry for this complex. The

electronic spectrum of Ni(II)- complex exhibited three bands in the region 19880, 29239 and 36630

cm-1

corresponding to the transitions 3A2g →3T2g,

3A2g→3T1g and (LMCT) respectively for octahedral geometry[22]. The magnetic moment value

of this complex was found 3.23 BM which was very close to the value of a distorted octahedral

environment. [21-22] .The electronic spectrum of Cd (II) complex exhibited two bands in the region

271nm(36900cm-1

) and 344nm(29069 cm-1

) corresponding to the Cd (II) complex is diamagnetic in



Vol.17, 2013

27

nature and its electronic spectra do not furnish any characteristic d-d transitions except charge

transfer (CT) bands as expected for d10 systems. [21-22]

Antibacterial Activities:

The zone inhibition of bacterial growth were measured in mm depending upon the diameter as

shown in Table (4) Figure. (2)The antibacterial activity results revealed that the ligands and there

complexes shown weak to good activity when compared to the Control (DMF) . [21-22]

It is evident from the above data that the antibacterial activity significantly increased on

coordination. This enhancement in the activity may be rationalized on the basis of their structures

mainly possessing an additional azomethine bond. It has been suggested that the ligand with

nitrogen and oxygen donor

systems inhibit enzyme activity. Coordination reduces the polarity of the metal ion mainly because

of the partial sharing of its positive charge with the donor groups within the chelate ring

system..[23- 24]

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851(2004).

6- Y.Miwa, Mizuno T., Tsuchiya K., Taga T and Iwata Y Synthesis and Characterization of

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53–60 (2003).



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9.Hana Bashir Shawish, Mohd Jamil Maah and Siti Nadia Abdul Halim, Synthesis and

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Appl. 1–10.(2006). 19.Liwang Jiwen Cai, Zon-Wang Mao, Xiao-Long Feng and Jim- Wang Huang, nickel complexes

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23. Taghreed H. Al-Noor, Sajed. M. Lateef and Mazin H. Rhayma, Synthesis, Characterization,

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24.Sarika Verma, Sarita Shrivastva and Poonam Rani , Synthesis and spectroscopic studies of

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able (1) The physical properties of the compounds

% Metal

Experiment

%Metal

Theory Cl%

ΛΛΛΛm

ohm-1

cm2 mol

-1

M .p (de) °c Color M .wt Compounds

- - - o.78 180 yellow 300.3092 H2L= C16H12N2O4

- - - 0.70 132 white 122 NA= C6H6N2O

9.7 9.19 Nil

9.06 (de)162

green 597.48

[Mn(L) (NA)2]

C28H26MnN6O6

10.3 9.33 Nil 15.92 (de)146

Deep brown 598.38 [Fe(L) (NA)

2]

C28H26MnN6O6

10.1 9.80 Nil 7.96 (de)174

green 601.47 [Co (L) (NA)

2]

C28H26 Co N6O6

10.1 9.76 Nil 7.76 132 (de)

green 601.23 [Ni (L) (NA)

2]

C28H26 Ni N6O6

7.90 7.16 Nil 4.80 (de)154

yellow 654.95 [Cd (L) (NA)

2]

C28H26 Cd N6O6



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Table (2) FTIR spectral data of the Ligands and there complexes

M-N M- O

N–N C–O

C=O υυυυ (C=N)(CH)cyclic NH sym Compound

- - s 986 s1266 m1716 1625vs 2939 br-s3132 ligand

- - - - - 1634s 2969 3323br

-vs NA

430 555 1020s 1282vs m1716

1624vs 2943 3190 [Mn(L) (NA)

2]

445 617 1029m 1286vs m1716 1593s 2937 3361vs [Fe(L) (NA)2]

433 607 1022s 1280vs m1734 1618vs 2941 3190vs [Co (L) (NA)2]

418 518 1020s 1288vs m1734 1618vs 2945 3190vs [Ni (L) (NA)2]

433 603 1024s 1282vs m1780 1624vs 2943 3190vs [Cd (L) (NA)2]

Sym: symmetric, asy: asymmetric, str: stretching, v .s: very strong, s: strong, m: medium, w:week,

sh: shoulder



Vol.17, 2013

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Table (3) Electronic Spectral data, magnetic moment, of the studied complexes and two ligands

µµµµeff (BM) Assignments υυυυ′′′′(cm-1

) λ max(nm) Compounds

- n→π*

n→π*

2923

28011

342

357

ligand

- π→π* 36900

271

NA

5.04l

6A 1g 4T1g (4G)

6A1g 4T2g (4G)

LMCT

14749

27932

29239

678

358

342

[Mn(L) (NA)2]

5.05

5T2g → 5E2g

LMCT

LMCT

14880

27932

29239

672

358

342

[Fe(L) (NA)2]

4.12

4T1g →4T2g(F)

LMCT

LMCT

1 4947

28011

29239

669

357

342

[Co (L) (NA)2]

3.23

3A2g →3T2g

3A2g→3T1g

LMCT

19880

29239 36630

503

342

273

[Ni (L) (NA)2]

0.00

Diamag

CT

CT

36900

29069

271

344

[Cd (L) (NA)2]



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Table (4) Showed the inhibition circle diameter in millimeter for the bacteria after24 hour

incubation paid and 37°°°°C for complexes

Bacillus

Staphylococcus Pseudomonas E .coli Compounds

5 5 5 5 Control(DMF)

10 7 8 8 Ligand (No-1)

12 12 9 10 NA(No -2)

7 10 8 7 [Mn(L) (NA)2]

14 23 15 11 [Fe(L) (NA)2]

13 12 12 14 [Co (L) (NA)2]

14 15 13 13 [Ni (L) (NA)2]

16 18 17 17 [Cd (L) (NA)2]



Vol.17, 2013

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